Ligand K-edge

Ligand K-edge spectroscopy is a spectroscopic technique used to study the electronic structures of metal-ligand complexes.^[1] This method measures X-ray absorption caused by the excitation of ligand 1s electrons to unfilled p orbitals (principal quantum number n <= 4) and continuum states, which creates a characteristic absorption feature called the K-edge.

Pre-edges

Transitions at energies lower than the edge can occur, provided they lead to orbitals with some ligand p character; these features are called pre-edges. Pre-edge intensities (D₀) are related to the amount of ligand (L) character in the unfilled orbital:

$D_{0}(L\ 1s\rightarrow \psi ^{*})=const\ \vert \langle L\ 1s\vert \mathbf {r} \vert \psi ^{*}\rangle \vert ^{2}=\alpha ^{2}\ const\ \vert \langle L\ 1s\vert \mathbf {r} \vert L\ np\rangle \vert ^{2}$

where $\psi ^{*}$ is the wavefunction of the unfilled orbital, r is the transition dipole operator, and $\alpha ^{2}$ is the "covalency" or ligand character in the orbital. Since $\psi ^{*}={\sqrt {1-\alpha ^{2}}}\vert M_{d}\rangle -\alpha \vert L_{np}\rangle$ , the above expression relating intensity and quantum transition operators can be simplified to use experimental values:

$D_{0}={\frac {\alpha ^{2}h}{3n}}I_{s}$

where n is the number of absorbing ligand atoms, h is the number of holes, and I_s is the transition dipole integral which can be determined experimentally. Therefore, by measuring the intensity of pre-edges, it is possible to experimentally determine the amount of ligand character in a molecular orbital.

References

↑ Solomon, E.; Hedman, B.; Hodgson, K.; Dey, A.; Szilagyi, R. (2005). "Ligand K-edge X-ray absorption spectroscopy: covalency of ligand–metal bonds". Coordination Chemistry Reviews. 249: 97–76. doi:10.1016/j.ccr.2004.03.020.

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Ligand K-edge

Pre-edges

See also

References